Process for making a thermoplastic vulcanizates

ABSTRACT

A process for making a thermoplastic vulcanizate (TPV) in a reactor is provided wherein a mixture is formed in which a silane grafted resilient polymer component is dispersed in a thermoplastic matrix component. The mixture is formed by mixing in a reactor a) from 25 to 60 parts by weight of a resilient polymer component per 100 parts by weight of the matrix component and resilient polymer component combined, b) from 40 to 75 parts by weight of a matrix component, per 100 parts by weight of the matrix component and resilient polymer component combined; and c) a silane grafting agent. The silane grafted resilient polymer component is crosslinked by adding a solid water-generating agent to the reactor.

1. FIELD OF THE INVENTION

This invention relates generally to a process for making thermoplasticvulcanizates to be used, for example, in automotive applications and asPVC replacements.

2. BACKGROUND

A thermoplastic vulcanizate (“TPV”) is generally known to be areprocessable material that has at least one partially or fullycrosslinked rubber or elastomer component dispersed in a thermoplasticmatrix component. Generally, TPVs are prepared by blending the materialsfor the matrix and elastomer components along with desired additives anda sulfur or peroxide cure package to promote at least partialcrosslinking of the elastomer component. The blending is performed in alarge scale mixer and the grafting is performed with the aid ofunsaturated functionality in the polymer chains of the elastomer,provided by units derived from dienes such as ethylidene norbornene.

The mixers are continuous and the TPV is provided in the form ofpellets. Upon reaching temperatures above the softening point or meltingpoint of the matrix component, a TPV can form continuous sheets and/ormolded articles with complete knitting or fusion of the TPV underconventional molding or shaping conditions for thermoplastics. A TPVpossesses the properties of a thermoset elastomer and is re-processablein an internal mixer.

In practical use, known procedures for making and converting TPV's intoa shaped article have limitations. For example, it is difficult toconvert polymers not having units derived from dienes. The overallprocess has many steps with the TPV supplied by a TPV manufacturer froma limited grade-slate, restricting adaptations of the formulation tospecific end use requirements.

It is known to graft polyolefins with silanes in, for example,electrical applications, and to allow moisture to effect cross-linkingsubsequent to extrusion.

Polymer Engineering and Science, June 1999, Vol. 39, No. 6, beginning onpage 1087 discloses a TPV with an ethylene-octene dispersed in apolypropylene matrix. In a first step, the ethylene-octene polymers arecoated and peroxide generation upon melting causes grafting (See PolymerEngineering and Science at page 1092). The polypropylene appropriatelycoated is added and blended in a second step. In a third step, water isinjected to effect cross-linking. DE4402943 discloses a similar process.

PCT publication WO 98/23687 discloses thermoplastic polymer blendcompositions that include a thermoplastic matrix resin phase that issubstantially free of cross-linking and a dispersed silane-graftedelastomer phase.

It is among the objects of the invention to provide a simplified and/orflexible process by integrating blending and grafting and/or blendingand curing.

3. SUMMARY OF THE INVENTION

In one embodiment, the present invention provides a process for making athermoplastic vulcanizate (“TPV”) in a reactor. The process includesforming a mixture in which a silane grafted resilient polymer componentis dispersed in a thermoplastic matrix component and adding a solidwater-generating agent to crosslink the silane grafted elastomercomponent. The mixture is formed by mixing in the reactor: a) from 40 to75 parts by weight of the matrix component, per 100 parts by weight ofthe matrix component and resilient polymer component combined, b) from25 to 60 parts by weight of the resilient polymer component, per 100parts by weight of the matrix component and resilient polymer componentcombined, and c) a silane grafting agent.

In another embodiment, the process includes a) blending a thermoplasticpolymer component for forming a continuous matrix phase, a resilientpolymer component, and a silane grafting agent for forming a phasedispersed in the matrix, and additives so as to promote silane grafting;and b) adding a solid water generating agent, which releases water,while the blend formed in step a) is submitted to shear so as tocrosslink the silane grafted polymer.

In a particular aspect of any of the embodiments described herein, theprocess has one or more of the following characteristics, in anycombination:

-   -   a) a continuous matrix phase having a crystallinity as        determined by DSC of at least 40%;    -   b) a resilient polymer component having a crystallinity as        determined by DSC of less than 40%;    -   c) the process further comprises mixing a free radical generator        in the reactor;    -   d) the free radical generator is a peroxide;    -   e) the process further comprises mixing a hydrolysis catalyst in        the reactor;    -   f) the silane grafting agent, free radical generator, and        hydrolysis catalyst are added as individual components to the        reactor;    -   g) the silane grafting agent, free radical generator, and        hydrolysis catalyst are added to the reactor as a mixture on a        porous carrier polymer;    -   h) the porous carrier polymer is selected from the group        consisting of polyethylene and polypropylene;    -   i) the silane grafting agent is a vinylalkoxysilane;    -   j) the vinylalkoxysilane is selected from the group consisting        of vinylmethoxysilane and vinylethoxysilane;    -   k) the solid water-generating agent is selected from the group        consisting of a metal oxide/carboxylic acid combination, Epsom        salt, Glauber's salt, clay, water, talc, and combinations        thereof;    -   l) the matrix component comprises at least one of a polyolefin,        a polyamide, and a polyester;    -   m) the resilient polymer component comprises at least one of        halobutyl rubber, ethylene-propylene rubber,        ethylene-propylene-diene terpolymer rubber, natural rubber,        synthetic rubber, amine functionalized synthetic rubber, and        epoxy functionalized synthetic rubber;    -   n) the resilient polymer component is an ethylene interpolymer;    -   o) the process includes mixing from 25 to 35 parts, or 30 parts,        by weight of the resilient polymer component and from 65 to 75        parts, or 70 parts, by weight of the matrix component, per 100        parts by weight of the matrix component and resilient polymer        component combined;    -   p) the reactor is a batch-type compounding apparatus;    -   q) the reactor is a continuous-type compounding apparatus;    -   r) the reactor is connected to a die suitable for extruding the        product in the reactor into a shaped, fabricated product without        an intervening pelletization step;    -   s) the matrix component has a crystallinity as determined by DSC        of at least 40%;    -   t) the resilient polymer component has a crystallinity as        determined by DSC of no more than 40%;    -   u) the crystallinity of the matrix component and the resilient        polymer component differ by at least 10%, or at least 20%; and    -   v) the matrix component and the resilient polymer component are        blended and simultaneously combined with the silane grafting        agent.

4. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the thermogravimetric analysis of weight lossversus temperature for magnesium sulfate hepthydrate (Epsom salt).

FIG. 2 is a graph of the thermogravimetric analysis of weight lossversus temperature for sodium sulfate decahydrate (Glauber's salt).

FIG. 3 is a graph of the thermogravimetric analysis of weight lossversus temperature for talc.

FIG. 4 is a graph of the thermogravimetric analysis of weight lossversus temperature for hydrated clay (hydrous aluminum silicate).

FIG. 5 is the thermogravimetric analysis of weight loss versustemperature for a zinc oxide/stearic acid combination.

FIG. 6 is the thermogravimetric analysis of weight loss versustemperature for a zinc oxide/isononanoic acid combination.

FIG. 7 is the thermogravimetric analysis of weight loss versustemperature for a zinc oxide/isooctanoic acid combination.

FIG. 8 is a low voltage SEM micrograph of calendared sheeting.

5. DETAILED DESCRIPTION

Thermoplastic Matrix Component

The matrix component of the TPV comprises a thermoplastic, for example,polyolefins, polyamides, and polyesters. Suitable polymers for thematrix component are those polyolefinic thermoplastic polymers made bythe polymerization of mono-olefin monomers using a high pressure, lowpressure or intermediate pressure process with conventional ZieglerNatta and/or single site catalysts such as metallocenes. Preferablythermoplastic matrix component is a polyolefin in which the monoolefinmonomers converted to repeat units are at least 95 wt % monoolefins ofthe formula CH₂═C(CH₃)—R or CH₂═CHR where R is a H or a linear orbranched alkyl group of from 1 to 12 carbon atoms.

Suitable polymers for the matrix component include polyethylene, andethylene interpolymers comprising as a comonomer an alpha olefin havingfrom 3 to 10 carbon atoms, polypropylene, propylene interpolymers withcomprising as a comonomer alpha olefins such as ethylene and alphaolefins having from 4 to 10 carbon atoms, as well as mixtures of two ormore. The ethylene derived polymer can be either high density or lowdensity. The term polypropylene is used to mean a homopolymer orcopolymer or mixtures thereof. Generally, the higher the meltingtemperature of the matrix component the higher the potential temperatureat which the TPV can be processed. The propylene polymer matrixcomponent can be any propylene-based polymer, i.e., a polymer wherein amajority of units are derived from propylene.

In one embodiment, the matrix component is based on a propylene polymerwhich may be a propylene homopolymer, a copolymer or an impactcopolymer. Generally, the propylene polymer may have a melt flow rate(MFR) of 15 or higher, and optionally an MFR of 25 or higher, or 35.Generally, the flexural modulus is at least 1000 MPa, or at least 1200MPa, or 1300 MPa. The polypropylene polymer can be made using amultiple-site catalyst or a single-site catalyst such as a metallocene.

In one embodiment, the matrix component is an impact modifiedpolypropylene. In this embodiment, the matrix component itself is ablend of a propylene polymer matrix with an uncrosslinked elastomerdispersed therein. In a particular aspect of this embodiment, theelastomer is a copolymer and is present in amount of less than 20 wt %based on the total weight of the impact modified polypropylene blend. Inanother particular aspect of this embodiment, the propylene polymermatrix component of the impact modified polypropylene is a polypropylenehaving a propylene content of at least 95 wt %, a weight averagemolecular weight of at least 70,000, and is highly stereoregular, witheither isotactic or syndiotactic regularity.

The impact modified polypropylene may be prepared as a reactor blendwherein the propylene polymer portion and the elastomer portion aresimultaneously formed by polymerization of propylene with anotherappropriate olefin comonomer in different zones or in a single reactionzone as is known in the art. Alternatively, the impact modifiedpolypropylene may be formed by melt compounding of a polypropylene withan elastomer, each of which were separately formed prior to blending.Generally, for reasons of economy, impact modified polypropylenes areprepared as reactor blends and for this reason generally have an impactmodifying elastomer content not exceeding 20 wt % of the reactor blend,and more typically not exceeding 12 wt % of the reactor blend. Furtherdiscussion of the particulars of an impact modified polypropylene may befound in U.S. Pat. No. 4,521,566, fully incorporated herein byreference. Regardless of how the impact modified polypropylene isformed, it generally comprises from 80 wt % to 90 wt % of a propylenepolymer and from 10 wt % to 20 wt % of an elastomer such that thepropylene content of the blend is at least 80 wt %. The impact modifiedpolypropylenes of the present invention have a 1% secant modulus of from60,000 psi to 130,000 psi, and a MFR within the range having an upperlimit of 5.0 or 3 and a lower limit of 0.5.

In one embodiment, the matrix component is a thermoplastic polyamidecomposition. These generally comprise crystalline or resinous, highmolecular weight solid polymers including copolymers and terpolymershaving recurring polyamide units within the polymer chain. Polyamidesmay be prepared by polymerization of one or more epsilon lactams such ascaprolactam, pyrrolidone, lauryllactam and aminoundecanoic lactam, oramino acid, or by condensation of dibasic acids and diamines. Both fiberforming and molding grade nylons are suitable. Examples of suchpolyamides are polycaprolactam (nylon 6), polylaurylactam (nylon 12),polyhexamethyleneadipamide (nylon 6,6), polyhexamethylene-azelamide(nylon 6,9), polyhexamethylenesebacamide (nylon 6,10),polyhexamethyleneisophthalamide (nylon 6,IP) and the condensationproduct of 11-aminoundecanoic acid (nylon 11); as well as partiallyaromatic polyamides made by polycondensation of meta xylene diamine andadipic acid. Furthermore, the polyamides may be reinforced, for example,by glass fibers or mineral fillers or mixtures thereof. Pigments, suchas carbon black or iron oxide may also be added. Additional examples ofpolyamides are described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, v. 10, page 919, and Encyclopedia of Polymer Science andTechnology, Vol. 10, pages 392-414.

The matrix component is present in an amount within the range having anupper limit of 80, or 75, or 70, or 65 parts by weight, and a lowerlimit of 40 parts by weight, per 100 parts by weight of the matrixcomponent and resilient polymer component combined. The resilientpolymer component is present in an amount within the range having anupper limit of 60 parts by weight, and a lower limit of 35, or 30, or25, or 20 by weight, per 100 parts by weight of the matrix component andresilient polymer component combined.

Resilient Polymer Component

The resilient polymer component generally comprises a polymer havingelastomeric properties. Examples include rubbers, elastomers, andplastomers. The polymer may have residual unsaturation or curablefunctional sites that can react and be at least partially crosslinkedwith curing agents. Possible materials for the rubber component includehalobutyl rubber, ethylene-propylene (EP) rubbers,ethylene-propylene-diene terpolymer (EPDM) rubbers, natural rubber, andsynthetic rubbers such as synthetic polyisoprene, polybutadiene rubber,styrene-butadiene rubber, butadiene-acrylonitrile rubber. Also suitableare amine functionalized or epoxy functionalized synthetic rubbers.Examples of these include amine functionalized EPDM, epoxyfunctionalized natural rubber, and functionalized metallocene plastomer.

The resilient polymer component may be based on an ethyleneinterpolymer, i.e., ethylene-derived units are the major constituent byweight %. The ethylene interpolymers may have a density within the rangehaving an upper limit of 0.915 g/cm³ or 0.910 g/cm³ and a lower limit of0.860 g/cm³. The ethylene interpolymer may be prepared with a singlesited catalyst, for example, a catalyst having a transition metalcomponent which is an organometallic compound with at least one ligandwhich has a cyclopentadienyl anion structure through which the ligandcoordinates to the transition metal cation. Preferably, the interpolymerhas a narrow molecular weight distribution and narrow compositionaldistribution.

Metallocene-catalyzed ethylene interpolymers may be partiallythermoplastic-like and partially elastomer-like, and are sometimesreferred to as “plastomers.” The ethylene interpolymer may be acopolymer having, based on total monomer content, from 85 mole % to 96mole % ethylene-derived units and 4 mole % to 15 mole % units derivedfrom alpha-olefin comonomer. The alpha-olefin comonomer is incorporatedin an amount that provides for a density of from 0.915 g/cm³ to 0.860g/cm³. The alpha-olefin comonomer of the plastomer may be an acyclicmonoolefin, such as butene-1, pentene-1, hexene-1, octene-1, and4-methyl-pentene-1.

The resilient polymer component may be based on anethylene-alpha-olefin-diene terpolymer. Incorporation of certain amountsof diene monomer provides the resilient polymer component with furtherresidual unsaturation to allow further functionalization and/orcross-linking reactions or coupling of the resilient polymer componentin the final product. However, the invention can also be practiced togive satisfactory results when the resilient polymer component is anethylene interpolymer substantially free of dienes.

The ethylene interpolymers may be characterized by one or more of thefollowing:

-   -   (a) a DSC melting point curve that exhibits the occurrence of a        single melting point peak occurring in the region of 40° C. to        110° C. (second melt rundown);    -   (b) a weight average molecular weight value in the range of        70,000 to 130,000;    -   (c) a molecular weight distribution (Mw/Mn) value of 4.0 or        less, or 3.5 or less; and    -   (d) a 1% secant modulus not exceeding 15,000 and as low as 800        psi or less.

The resilient polymer component may be an EXACT™ plastomer, availablefrom ExxonMobil Chemical Company of Baytown, Tex. EXACT™ plastomers arecopolymers of ethylene and a C₄-C₈ alpha-olefin comonomer and have aplastic-like molecular weight.

The resilient polymer component may be an Engage™ polymer. Engage™polymers are metallocene-catalyzed plastomers, available from DowChemical Company of Midland, Mich.

The resilient polymer component may comprise two or more polymers. Forexample, the resilient polymer component may comprise (a) an ethylenecopolymer having a C₄-C₈ alpha-olefin comonomer and a plastic-likemolecular weight, such as the EXACT™ plastomers described above, and (b)an ethylene-propylene-diene (“EPDM”) terpolymer. The EPDM of (b) may bea low crystallinity EPDM present in the resilient polymer component inan amount within the range having an upper limit of 75 wt % or 70 wt %and a lower limit of 50 wt % or 60 wt %, based on the total weight ofthe resilient polymer component, and having a density within the rangehaving an upper limit of 0.90 g/cm³, or 0.880 g/cm³ and a lower limit of0.860 g/cm³. By low crystallinity EPDM, it is meant that the EPDM has aheat of fusion less than 10 J/g, as determined by DSC. The lowcrystallinity EPDM may be Vistalon™ 7500, available from ExxonMobilChemical Company of Baytown, Tex. Vistalon™ 7500 is a low crystallinityEPDM terpolymer having an ethylene content of 52.3 wt % and a heat offusion of 0.6 J/g.

Alternatively, the EPDM of component (b) may be a high crystallinityEPDM present in the resilient polymer component in an amount within therange having an upper limit of 60 wt % or 50 wt % and a lower limit of20 wt % or 25 wt %, based on the total weight of the resilient polymercomponent. By high crystallinity EPDM, it is meant that the EPDM has anethylene content of more than 70 wt % and a heat of fusion more than 10J/g, as measured by DSC. The high crystallinity EPDM may be Vistalon™1703P, available from ExxonMobil Chemical Company of Baytown, Tex.Vistalon™ 7500 is a high crystallinity EPDM having an ethylene contentof 78% and a vinyl norbornene content of 0.9 wt %.

The rubber component may further comprise a halogenated copolymer ofisomonoolefin and alkylstyrene as described in U.S. Pat. Nos. 5,162,445and 6,207,754, both fully incorporated herein by reference. Thehalogenated copolymer may be a copolymer of a C₄ to C₇ isomonoolefin andan alkylstyrene. The isomonoolefin may be isobutylene, the alkylstyrenemay be halogenated methylstyrene, and the halogen may be bromine. Thehalogenated copolymer may be produced by halogenating anisobutylene-alkylstyrene copolymer using bromine in normal alkane (e.g.,hexane or heptane) solution utilizing a bis azo initiator, e.g., AIBN orVAZO 52 (2,21-azobis(2,4 dimethylpentane nitrile)), at 55° C. to 80° C.for a time period ranging from 4.5 to 30 minutes, followed by a causticquench. The recovered polymer is then washed in basic water wash andwater/isopropanol washes, recovered, stabilized and dried.

Crosslinking

One common method of crosslinking involves the use of peroxide to formcarbon to carbon bonds to crosslink the resilient polymer component.When the matrix component comprises polypropylene, however, the peroxidedegrade the polypropylene matrix in addition to crosslinking theresilient polymer component. Thus, it is desirable to use a chemicalagent that will significantly crosslink the elastomer component, such asa vinylalkoxysilane. Vinyltrimethoxysilane (VTMOS) andvinyltriethoxysilane (VTEOS) are specific examples ofvinylalkoxysilanes. Vinylalkoxysilanes can be used in conjunction with avery small amount of peroxide, i.e., a ratio ofvinylalkoxysilane/peroxide of from 10/1 to 40/1. The peroxide can beselected to be reactive at a low temperature during the initialblending. The peroxide is used as a free radical generator to graft thevinylsilane molecules onto the elastomer backbone, as shown below.

The invention can be practiced by adding to the compounding apparatus,during the grafting stage, the silane and optionally a free radicalgenerator and hydrolysis catalyst as individual components, or as amixture.

The silane may be fed into the compounding apparatus via a solid carrierpolymer which is compatible with the base polymer. Such a process isdescribed in U.S. Pat. No. 5,112,919, fully incorporated herein byreference, which provides a process for adding a solid feed of silanecrosslinking agent into an extruder, as opposed to liquid silane.

The silane may be fed as a “silane masterbatch” into the compoundingapparatus. The term “silane masterbatch” as used herein refers to amixture of a vinylalkoxysilane, a small amount of free radicalgenerator, and a hydrolysis catalyst on a solid carrier polymer. Twotypes of silane masterbatch are commercially available. One type isbased on a porous polyethylene carrier, and the other type is based on aporous polypropylene carrier. The polypropylene carrier may be ahomopolypropylene, impact copolymer of propylene, or random copolymer ofpropylene. Polypropylene random copolymers are not preferred becausevinylsilane will graft onto the ethylene linkages along the backbone ofthe polypropylene random copolymer and crosslink both the carrier aswell as the elastomer.

Engineering resins, such as polyamide and polyesters, may also be usedas the carrier in order to increase the high temperature resistance ofthe TPV. Maleic anhydride grafted plastomers or maleic anhydride graftedEP rubber or EPDM can be used as a compatibilizer between theengineering resin and the resilient polymer component. Peroxide andvinylsilane can also be used as the carrier.

When the silane grafting reaction is complete, a water-generating agentreleases water upon heating, and preferably at the melting temperaturerange of the polymers, inside the compounding equipment, which enablesthe crosslinking to occur. The water-generating agent can be added tothe reactor upon completion of the silane grafting reaction. Examples ofwater-generating agents include Epsom salt, Glauber's salt, clay, water,talc, metal oxide/carboxylic acid combinations, and combinationsthereof. Examples of metal oxide/carboxylic acid combinations are zincoxide/stearic acid, zinc oxide/isononaioc acid, and zinc oxideisooctanoic acid.

FIGS. 1 and 2 illustrate the thermogravimetric analysis of weight lossversus temperature for magnesium sulfate hepthydrate (Epsom salt), andsodium sulfate decahydrate (Glauber's salt), respectively. The figuresshow that Epsom salt releases half of its hydrated water at 150° C. to200° C. and Glauber's salt releases half of its hydrated water at a muchlower temperature. FIGS. 3-7 illustrate the thermogravimetric analysisof weight loss versus temperature for talc, hydrated clay (hydrousaluminum silicate), and several metal oxide/carboxylic acid combinations(zinc oxide/stearic acid, zinc oxide/isononanoic acid, and zincoxide/isooctanoic acid).

In the presence of water molecules, the OR groups of the graftedvinylsilane molecules can be easily hydrolyzed into OH groups. The Si—OHgroups can then undergo a condensation reaction in the presence of ahydrolysis catalyst, for example dibutyltin dilaurate, to form Si—O—Silinkages. When there are not enough vinylsilane molecules grafted ontothe elastomer backbone, the Si—O—Si linkages provide two dimensionalchain extensions from the elastomer molecules. When there are enoughvinylsilane molecules grafted onto the elastomer backbone, a threedimensional network can be formed, and the elastomers are crosslinked.The crosslinking process described above is shown below.

The invention can be practiced without a subsequent vulcanization step,because the addition of the water-generating agent to the compoundingapparatus allows the TPV to be crosslinked before emerging from thecompounding line. In the case of a batch mixer, after completing thegrafting reaction, the feed ram is raised and the water-generating agentis added. The mixing is then continued inside the mixer until thevulcanization reaction is complete. Alternatively, a continuous mixer,e.g. an extruder, can be used as the compounding apparatus. In aone-pass process, the water-generating agent is added to the extruder ata point downstream of the region where the silane grafting reactionoccurs. In a two-pass process, the silane grafting occurs in the firstpass, and the crosslinking reaction is completed by adding thewater-generating agent in a second pass on the same extruder.

By appropriate process conditions, the degree of crosslinking, i.e. gelcontent, may be substantially the same for the entire compound. This isan advantage over processes in which an article is crosslinked bysubjecting the compounded article to water after emerging from thecompounding line, which causes the degree of crosslinking to depend onthe thickness of the article.

Other Ingredients

The TPVs of the present invention may be modified by adding conventionalingredients known in the art. Such ingredients include, but are notlimited to particulate fillers, clay, pigments, reinforcing agents,stabilizers, antioxidants, flame retardants, tackifiers, plasticizers,waxes, processing oils, lubricants, foaming agents, and extender oils.These additional ingredients can comprise up to about 50 weight percentof the total composition. Those of skill in the art will appreciate thatother additives may be used to enhance properties of the TPV.

Apparatus

The TPVs of the present invention can be prepared using any suitablebatch-mixing apparatus (e.g., Banbury mixer) or continuous apparatus(e.g., a single screw or twin screw extruder).

EXAMPLES

The present invention is illustrated hereinafter in more detail withreference to the following examples, which should not be construed as tolimit the scope of the present invention. Table 1 provides a list of thetest methods used in the examples.

In the following examples, Escorene™ PP 1105 is a propylene homopolymerhaving a melt flow rate of 35, a flexural modulus (MPa) of 1300, and aNotched Izod Impact (@23° C. KJ/m²) of 3.2. Escorene™ PP 8191 is animpact modified polypropylene having a density of 0.9 g/cm³, a melt flowrate of 1 dg/min, an ethylene comonomer content of 20 wt %, a 1% secantmodulus of 62,500 psi and a DSC peak melting point of 141.6° C. Capron™CA 73 ZP is a polyamide-6 resin from Honeywell, Morristown, N.J. Ultamid35 is a polyamide 6,66 copolymer from BASF, Freeport, Tex. Pebax 3533 isa flexible polyamide from Atofina Chemical, Philadelphia, Pa. Sunpar 150HT is a processing oil from Sun Oil, Marcus Hook, Pa. Exact™ 8201 is anethylene-octene copolymer having a melt index of 1.1 g/10 min, a densityof 0.882 g/cm³, a flexural modulus 1% secant of 3300 psi, a Mooneyviscosity (1+4 @125° C.) of 19, a peak melting temperature of 66.7° C.,and a melt flow rate of 2.5 g/10 min. Exact™ 4033 is an ethylene-butenecopolymer having a density of 0.880 g/cm³, a melt index of 0.8 dg/10min., a flexural modulus 1% secant of 3300 psi, a Mooney viscosity (1+4@125° C.) of 28 and a DSC peak melting point of 60° C. Vistalon™ 1703Pis a high crystallinity EPDM containing about 0.9 wt % vinyl norborneneand 78 wt % ethylene. Vistalon™ 3666 is an oil extended low crystallineEPDM with 0 J/g heat of fusion. Vistalon™ 9303H is another lowcrystalline EPDM having a 3.7 J/g heat of fusion. Exxpro™ 89-1 is abrominated polymer derived from a copolymer of isobutylene andmethylstyrene. Exxpro™ 89-1 has a density of 0.93 g/cm³, a Mooneyviscosity of 35 ML (1+8) @ 125° C. and a bromine wt % of 1.2. Escorene™,Exact™, Vistalon™ and Exxpro™ are products available from ExxonMobilChemical Company. Silane masterbatch #1 was supplied by OSI Specialties,Crompton Corporation, Tarrytwon, N.J., under the designation of XL-PearlY-15307, which comprises 70 wt % of a silane mixture absorbed into 30 wt% porous polypropylene. The majority of the silane mixture comprises aVTMOS type of silane with grafting peroxide and hydrolysis catalystadded. Silane masterbatch #2, also supplied by OSI Specialties comprises50 wt % of a silane mixture absorbed into 50 wt % porous polyethylene.The majority of the silane mixture comprises a VTMOS type of silane.Silane masterbatch #3, also supplied by OSI comprises 70 wt % of asilane mixture absorbed into 30 wt % porous polypropylene. The majorityof the silane mixture comprises a VTEOS type of silane. A commercialsupplier of porous carrier is Accurel Systems, Akzo Nobel Membrana Gmbh,Obemburg, Germany. TABLE 1 Test Method Melt Flow Rate ASTM D1238 ShoreHardness ASTM D2240 Conditioning of Test Specimens ASTM D618 TensileStrength ASTM D638 Tensile Modulus ASTM D638 Ultimate Elongation ASTMD638 Flexural Modulus ASTM D790 DSC Peak Melting Point ASTM D3417 GelContent ASTM D-2765 Compression Set ASTM D-395

Example 1 Banbury Mixer; Silane Masterbatch #1

In Samples 1-5, various amounts of silane masterbatch #1 (VTMOS typesilane absorbed on a porous polypropylene carrier) were added to 30/70blends of Escorene™ PP 1105/Exact™ 8201 and the mixture melt mixed in a0° C. size Banbury mixer to perform a silane grafting reaction. A batchweight of 2270 grams was used. After the silane grafting reaction wascompleted, as indicated by a motor torque increase, the feed ram wasraised, and 0.2 parts of Epsom salt per hundred parts of resin wasadded. The ram was then lowered until another torque increase wasobserved. In order to prevent the material from being heated up to above500° F., the mixer was shifted to a lower rotor speed to complete thecrosslinking reaction. TABLE 2 Sample 1 Sample 2 Sample 3 Sample 4Sample 5 Composition Escorene ™ PP 1105 30 30 30 30 30 (parts per 100parts of Escorene ™ PP 1105 and EXACT ™ 8201 combined) EXACT ™ 8201 7070 70 70 70 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™ 8201combined) Silane Masterbatch #1 1.5 2 2.5 3 3.5 (parts per 100 parts ofEscorene ™ PP 1105 and EXACT ™ 8201 combined) Epsom Salt 0.2 0.2 0.2 0.20.2 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™ 8201combined) Property Hardness (Shore D) @ 0 sec Elapsed Time 47 47 49 4948 @ 15 sec Elapsed Time 43 43 44 44 42 Tensile Stress (psi) 100%Modulus 1337 1272 1267 1165 1187 200% Modulus 1464 1421 1445 1324 1375300% Modulus 1556 1548 1598 1472 1549 Ultimate 2497 2297 2207 2322 2293Ultimate Elongation (%) 1167 832 665 742 663 Flexural Modulus (psi)Tangent 19804 19163 16369 15791 15257 1% Secant 19308 18561 15994 1536014840 Tear Strength (lb/in) @ Max Load 484.4 418 364.8 341.7 348.8 @Break 241 249.5 214.6 173.6 248.9 Compression Set (%) @ 70° C. & 22 hrs83 77 74 70 72 Xylene Extractables (%) 31.97 46.24 50.3 59.77 59.82

Example 2 Twin Screw Extruder; Silane Masterbatch #1

Samples 6-11 of Table 3 illustrate TPVs having a propylene homopolymermatrix component and an ethylene based copolymer rubber componentproduced by a continuous mixer, as described in detail below. The sameresin mixture of Escorene™ PP 1105/Exact™ 8201 as described in Example1, together with the VTMOS masterbatch on a porous polypropylene carrieris first melt compounded using a 30 mm ZSK twin screw extruder tocomplete the silane grafting reaction. In a second pass, the meltblended compound together with Epsom salt was compounded on the same ZSKextruder to complete the crosslinking reaction. TABLE 3 Sample 6 Sample7 Sample 8 Sample 9 Sample 10 Sample 11 Composition Escorene ™ PP 110530 30 30 30 30 30 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™8201 combined) Exact ™ 8201 70 70 70 70 70 70 (parts per 100 parts ofEscorene ™ PP 1105 and EXACT ™ 8201 combined) Silane Masterbatch #1 22.5 3 3.5 4 4.5 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™8201 combined) Epsom Salt 0.2 0.2 0.2 0.2 0.2 0.2 (parts per 100 partsof Escorene ™ PP 1105 and EXACT ™ 8201 combined) Property Hardness(Shore D) @ 0 sec Elapsed Time 47 46 46 45 47 46 @ 15 sec Elapsed Time42 41 42 40 42 40 Tensile Stress (psi) 100% Modulus 1267 1180 1221 11901224 1248 200% Modulus 1387 1325 1395 1460 1497 1545 300% Modulus 14771448 1542 1698 1674 1751 Ultimate 2500 2400 2462 1766 1870 1893 UltimateElongation (%) 1142 923 879 345 369 346 Flexural Modulus (psi) Tangent18466 17703 16547 15701 15725 15383 1% Secant 18442 17501 16523 1531015482 15222 Tear Strength (lb/in) @ Max Load 444 397 392 356 349 342 @Break 265 216 218 217 224 202 Compression Set (%) @ 70° C. & 22 hrs 8078 72 76 66 66 Vicat Softening Point @ 1000 g 74.9 75.3 75.8 86.4 86.897.1 Xylene Extractables (%) 39.12 52.62 54.24 63.83 64.56 65.4

Example 3 Banbury Mixer; Silane Masterbatch #2

In Samples 12-16, various amounts of VTMOS masterbatch on a porouspolyethylene carrier (from 1.5 parts per hundred to 3.5 parts perhundred resin) were added to 30/70 blends of Escorene™ PP 1105/Exact™8201 and the mixture melt mixed in a 00C size Banbury mixer to perform asilane grafting reaction. A batch weight of 2270 grams was used. Afterthe silane grafting reaction was completed, as indicated by a motortorque increase, the feed ram was raised, and 0.2 parts of Epsom saltper hundred parts of resin was added. The ram was then lowered untilanother torque increase was observed. In order to prevent the materialfrom being heated up to above 500° F., the mixer was shifted to a lowerrotor speed to complete the crosslinking reaction. TABLE 4 Sample 12Sample 13 Sample 14 Sample 15 Sample 16 Composition Escorene ™ PP 110530 30 30 30 30 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™8201 combined) EXACT ™ 8201 70 70 70 70 70 (parts per 100 parts ofEscorene ™ PP 1105 and EXACT ™ 8201 combined) Silane Masterbatch #2 1.52 2.5 3 3.5 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™ 8201combined) Epsom Salt 0.2 0.2 0.2 0.2 0.2 (parts per 100 parts ofEscorene ™ PP 1105 and EXACT ™ 8201 combined) Property Hardness (ShoreD) @ 0 sec Elapsed Time 48 47 49 47 47 @ 15 sec Elapsed Time 43 43 45 4343 Tensile Stress (psi) 100% Modulus 1309 1250 1267 1155 1161 200%Modulus 1333 1339 1381 1245 1243 300% Modulus 1359 1401 1466 1324 1317Ultimate 2503 2435 2434 2442 2477 Ultimate Elongation (%) 1373 1287 12231129 1201 Flexural Modulus (psi) Tangent 25211 21845 24782 20444 204321% Secant 23894 20965 23395 19567 19861 Tear Strength (lb/in) @ Max Load506.2 517.3 500.7 439.3 480.1 @ Break 245.7 265.9 287.6 258.7 280.3Tension Set (%) @200% & min. 69 67 63 69 69 Compression Set (%) @ 70° C.& 22 hrs 72 80 84 74 82 Vicat Softening Point @1000 g 75.8 79.7 81.578.7 74.9 Xylene Extractables (%) 0.265 22.17 23.69 36.23 35.75

Example 4 Twin Screw Extruder, Silane Masterbatch #2

Samples 17-24 of Table 5 illustrate TPVs having a propylene homopolymermatrix component and an ethylene based copolymer rubber componentproduced by a continuous mixer, as described in detail below. The sameresin mixture of Escorene™ PP 1105/Exact™ 8201 as described in Example1, together with the VTMOS masterbatch on a porous polyethylene carrieris first melt compounded using a 30 mm ZSK twin screw extruder tocomplete the silane grafting reaction. In a second pass, the meltblended compound together with Epsom salt was compounded on the same ZSKextruder to complete the crosslinking reaction. TABLE 5 Sample SampleSample Sample Sample Sample Sample Sample 17 18 19 20 21 22 23 24Composition Escorene ™ PP 1105 30 30 30 30 30 30 30 30 (parts per 100parts of Escorene ™ PP 1105 and EXACT ™ 8201 combined) Exact ™ 8201 7070 70 70 70 70 70 70 (parts per 100 parts of Escorene ™ PP 1105 andEXACT ™ 8201 combined) Silane Masterbatch #2 0.5 1 2 2.5 3 3.5 4 4.5(parts per 100 parts of Escorene ™ PP 1105 and EXACT ™ 8201 combined)Epsom Salt 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (parts per 100 parts ofEscorene ™ PP 1105 and EXACT ™ 8201 combined) Property Hardness (ShoreD) @ 0 sec Elapsed Time 45 46 47 47 45 47 48 48 @ 15 sec Elapsed Time 4041 42 42 41 42 43 42 Tensile Stress (psi) 100% Modulus 1232 1294 13291356 1303 1190 1229 1257 200% Modulus 1211 1373 1418 1458 1424 1324 14111477 300% Modulus 1230 1425 1472 1518 1499 1447 1570 1666 Ultimate 26572320 2517 2561 2472 2254 2130 2092 Ultimate Elongation (%) 1484 12051324 1331 1240 767 619 537 Flexural Modulus (psi) Tangent 28973 2496322105 21413 20437 19973 18123 18662 1% Secant 28622 24252 21840 2125320284 19257 17881 18248 Tear Strength (lb/in) @ Max Load 525 587 504 527504 401 386 392 @ Break 273 343 263 279 264 224 211 258 Tension Set (%)@200% & 5 min. 75 65 73 68 64 60 56 44 Compression Set (%) @ 70° C. & 22hrs 91 85 81 81 78 77 74 74 Vicat Softening Point @ 1000 g 74.9 76.177.6 77.3 78.6 81.1 80 84.8 Xylene Extractables (%) 0.22 0.23 0.12 1.6933.72 51.62 54.15 55.45

Example 5 Silane Masterbatch #3

In Samples 25-28, various amounts of vinylethoxysilane (VTEOS)masterbatch on a porous polypropylene carrier (from 0.5 parts perhundred to 2 parts per hundred resin) were added to 30/70 blends ofEscorene™ PP 1105/Exact™ 8201 and the mixture melt mixed in a 00C sizeBanbury mixer to perform a silane grafting reaction. A batch weight of2270 grams was used. After the silane grafting reaction was completed,as indicated by a motor torque increase, the feed ram was raised, and0.2 parts of Epsom salt per hundred parts of resin was added. The ramwas then lowered until another torque increase was observed. In order toprevent the material from being heated up to above 500° F., the mixerwas shifted to a lower rotor speed to complete the crosslinkingreaction.

The results show that the gel levels achieved with VTEOS are far lessthan with the corresponding VTMOS shown in Example 1. TABLE 6 SampleSample Composition 25 Sample 26 Sample 27 28 Escorene ™ PP 1105 30 30 3030 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™ 8201 combined)EXACT ™ 8201 70 70 70 70 (parts per 100 parts of Escorene ™ PP 1105 andEXACT ™ 8201 combined) Silane Masterbatch #3 0.5 1 1.5 2.0 (parts per100 parts of Escorene ™ PP 1105 and EXACT ™ 8201 combined) Epsom Salt0.2 0.2 0.2 0.2 (parts per 100 parts of Escorene ™ PP 1105 and EXACT ™8201 combined) Xylene Insolubles (%) 0.06 0.06 0.06 7.26

Example 6

Samples 29-34 illustrate TPVs having a propylene homopolymer matrixcomponent, and a rubber component comprising a combination of ametallocene plastomer and a low crystallinity EPDM rubber. Each of thesecompositions shows only a polypropylene melting peak by DSC, and nosecondary low temperature peak was observed. Also in Sample 31 theBurgess clay served as both a water-generation agent and a reinforcingagent as indicated by the higher tensile strength of the non-claycontaining compounds. TABLE 7 Sample 29 Sample 30 Sample 31 Sample 32Sample 33 Sample 34 Composition Escorene ™ PP 1105 30 30 30 30 30 30(parts per 100 parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistaloncombined) Exact ™ 8201 23 23 23 (parts per 100 parts of Escorene ™ PP1105, EXACT ™ 8201, and Vistalon combined) Vistalon ™ 3666 47 70 (partsper 100 parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistaloncombined) Vistalon ™ 7500 47 70 (parts per 100 parts of Escorene ™ PP1105, EXACT ™ 8201, and Vistalon combined) Vistalon ™ 9303H 47 70 (partsper 100 parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistaloncombined) Silane Masterbatch 3.4 3.4 3.4 3.4 3.4 3.4 (parts per 100parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistalon combined) Sunpar150 HT 10 10 10 10 (parts per 100 parts of Escorene ™ PP 1105, EXACT ™8201, and Vistalon combined) Epsom Salt 0.2 0.2 0.2 0.2 0.2 0.2 (partsper 100 parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistaloncombined) Burgess Clay 210 3.5 (parts per 100 parts of Escorene ™ PP1105, EXACT ™ 8201, and Vistalon combined) Property Hardness (Shore A 7978 78 71 78 74 @15 sec.) Ultimate Tensile (psi) 857 579 1065 486 831 602Elongation at Break (%) 316 321 745 206 622 410

Example 7

Samples 35-38 illustrate TPVs having a propylene homopolymer matrixcomponent, and a rubber component comprising a combination of ametallocene plastomer and a high crystallinity EPDM rubber. As shown inTable 8, the substitution of a high crystallinity EPDM such as Vistalon™1703P (78 wt % ethylene and 36.5 J/g heat of fusion) for EXACT™ 8201 inthis embodiment improves the softness (flexural modulus and hardness) ofthe TPV. Based on the gel content results, it is apparent thatvinylsaline can be simultaneously grafted to both EXACT™ 8201 andVistalon™ 1703P and crosslinked by the same type and amount ofwater-generating agent (Epsom salt).

The compositions in Table 8 were produced by two pass compounding usinga 30 mm ZSK twin screw extruder. All ingredients were first blendedtogether and fed into the extruder to complete the silane graftingreaction. In a second pass extrusion, Epsom salt was compounded togetherwith the materials produced from the first pass to complete thecrosslinking reaction. Samples 36-38 show a decrease in stiffness(flexural modulus), as compared to comparative sample 35, as moreVistalon™ 1703 P is used to replace the stiffer Exact™ 8201. TABLE 8Sample 35 Sample 36 Sample 37 Sample 38 Composition Escorene ™ PP 110530 30 30 30 (parts per 100 parts of Escorene ™ PP 1105, EXACT ™ 8201,and Vistalon combined) Exact ™ 8201 70 50 40 40 (parts per 100 parts ofEscorene ™ PP 1105, EXACT ™ 8201, and Vistalon combined) Vistalon ™1703P 20 30 30 (parts per 100 parts of Escorene ™ PP 1105, EXACT ™ 8201,and Vistalon combined) Silane Masterbatch #1 3 3 3 3 (parts per 100parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistalon combined) Sunpar150 HT 5 5 5 10 (parts per 100 parts of Escorene ™ PP 1105, EXACT ™8201, and Vistalon combined) Epsom Salt 0.2 0.2 0.2 0.2 (parts per 100parts of Escorene ™ PP 1105, EXACT ™ 8201, and Vistalon combined)Property Melt Flow Rate @ 2.9 4.2 8 10.3 10X wt (dg/min) Hardness (ShoreD) 48.4 45.2 42.2 32 Ultimate Tensile 1980 1785 1527 1090 Stress (psi)Elongation at Break 434 448 410 294 (%) Tensile Modulus (psi)  15% 330367 268 149 100% 1263 1125 1005 816 200% 1528 1354 1220 975 300% 17411542 1388 1042 Flexural Modulus, 1% 16855 14606 12584 9636 secant (psi)Tear Strength (lb/in) @ Max Load 359 363 319 302 @ Break 213 211 183 138Compression Set, 42.4 44 45.1 46 Room Temperature & 22 hr (%) TensionSet 100% 71 78 69 57 @Room Temperature (%) Xylene Insolubles (%) 58.6553.51 47.57 42.17

Example 8

In Samples 39-41, 2.2 parts per hundred resin of vinylmethoxysilane(VTMOS) masterbatch on a porous polypropylene carrier were added to27.6/64.6 blends of Escorene™ PP 7715E4/Exact™ 8201. In each of samples39-41, a different metal oxide/carboxylic acid combination was used.TABLE 9 Sample 39 Sample 40 Sample 41 Composition Escorene ™ PP 7715E427.6 27.6 27.6 (parts per 100 parts of Escorene ™ PP 7715E4 and EXACT ™8201 combined) EXACT ™ 8201 64.6 64.6 64.6 (parts per 100 parts ofEscorene ™ PP 7715E4 and EXACT ™ 8201 combined) Silane Masterbatch #12.2 2.2 2.2 (parts per 100 parts of Escorene ™ PP 7715E4 and EXACT ™8201 combined) Sunpar 150HT 5 5 5 (parts per 100 parts of Escorene ™ PP7715E4 and EXACT ™ 8201 combined) Zinc Oxide 0.3 0.3 0.3 (parts per 100parts of Escorene ™ PP 7715E4 and EXACT ™ 8201 combined) IsononanoicAcid 0.3 (parts per 100 parts of Escorene ™ PP 7715E4 and EXACT ™ 8201combined) Isooctanoic Acid 0.3 (parts per 100 parts of Escorene ™ PP7715E4 and EXACT ™ 8201 combined) Stearic Acid 0.3 (parts per 100 partsof Escorene ™ PP 7715E4 and EXACT ™ 8201 combined) Property Melt FlowRate @10X wt, 10.5 9.7 8.9 (dg/min) Hardness (Shore D) @ 15 sec ElapsedTime 40 41 39 Ultimate Tensile Stress (psi) 1298 1074 1299 Elongation @Break (%) 586 278 667 Tensile Modulus (psi)  50% 696 725 862 100% 856885 827 300% 1117 1166 1059 Tear Resistance (lb/in) @ Max Load 347 337352 Xylene Insolubles (%) 43.1 40.9 39.4

Example 9

In Sample 42, 3 parts per hundred resin of VTMOS masterbatch on a porouspolypropylene carrier was added to a 30/70 blend of Escorene™ PP1105/Exact™ 8201. In Sample 43, 3 parts per hundred resin of VTMOSmasterbatch on a porous polypropylene carrier was added to a 30/70 blendof Escorene™ 7715/Exact™ 8201. Escorene™ 7715 is an impact copolymerhaving a polypropylene matrix with an uncrosslinked ethylene-propylenedispersed therein. TABLE 10 Sample 42 Sample 43 Composition Escorene ™1105 30 (parts per 100 parts of Escorene ™ 1105, Escorene ™ PP 7715, andEXACT ™ 8201 combined) Escorene ™ 7715 30 (parts per 100 parts ofEscorene ™ 1105, Escorene ™ PP 7715, and EXACT ™ 8201 combined) EXACT ™8201 70 70 (parts per 100 parts of Escorene ™ 1105, Escorene ™ PP 7715,and EXACT ™ 8201 combined) Silane Masterbatch #1 3 3 (parts per 100parts of Escorene ™ 1105, Escorene ™ PP 7715, and EXACT ™ 8201 combined)Epsom Salt 0.2 0.2 (parts per 100 parts of Escorene ™ 1105, Escorene ™PP 7715, and EXACT ™ 8201 combined) Burgess Clay 201 3.5 3.5 (parts per100 parts of Escorene ™ 1105, Escorene ™ PP 7715, and EXACT ™ 8201combined) Property Density (g/cm³) 0.917 0.908 Melt Flow Rate (dg/min)0.59 0.97 Tensile Strength (psi)  10% Modulus, MD/TD 692/566 469/353 50% Modulus, MD/TD 1183/1031 835/696 100% Modulus, MD/TD 1287/1139949/793 300% Modulus, MD/TD 1546/1385 1172/1001 Break, MD/TD 3745/32892722/2163 Elongation @ Break (%) 1167/1170 1187/1121

Example 10

TPV compositions were prepared with an impact modified polypropylenecopolymer (Escorene™ PP 8191) as the matrix component, and a rubbercomponent comprising a metallocene plastomer (Exact™ 4033) and ahalogenated rubber (Exxpro™ 89-1), as shown in Table 11. TABLE 11 SampleSample 44 Sample 45 46 Composition Escorene ™ PP 8191 40 40 40 (partsper 100 parts of Escorene ™ PP8191, EXACT ™ 4033, and Exxpro ™89-1combined) Exact ™ 4033 55 55 47.5 (parts per 100 parts of Escorene ™PP8191, EXACT ™ 4033, and Exxpro ™ 89-1combined) Exxpro ™ 89-1 5 5 12.5(parts per 100 parts of Escorene ™ PP8191, EXACT ™ 4033, and Exxpro ™89-1combined) Zinc Oxide 0.05 0.2 (parts per 100 parts of Escorene ™PP8191, EXACT ™ 4033, and Exxpro ™ 89-1combined) Zinc Stearate 0.05 0.2(parts per 100 parts of Escorene ™ PP8191, EXACT ™ 4033, and Exxpro ™89-1combined) Property Melt Flow Rate @ wt, dg/min 1 0.9 0.1 FlexuralModulus, 1% secant, psi 23900 22000 20500

In the presence of zinc oxide and zinc stearate, the plastomer can begrafted onto the halogenated rubber. But the combination of zincoxide/zinc stearate is ineffective in crosslinking the plastomer,itself. The extra amount of zinc oxide and zinc stearate present can beused to crosslink the halogenated rubber. Sample 44 shows that bysubstituting 5 parts of the halogenated rubber for the plastomer, theresulting blend has a melt flow rate of 1 dg/min. Sample 45 is identicalto Sample 44, except that 0.05 parts of zinc oxide per hundred parts ofresin and 0.05 parts of zinc stearate per hundred parts resin wereadded. The resultant composition showed a slight decrease of melt flowrate due to crosslinking of the 5 parts of halogenated rubber. In Sample46, 12.5 parts of the halogenated rubber was used to replace an equalamount of the plastomer, and the melt flow rate decreased to 0.1 dg/min,indicating an increased degree of crosslinking in the compound.

Example 11

A 75 liter Banbury mixer was used to produce a TPV having a compositionas described in Table 12 below. EXACTS 8201, Escorene™ PP 1105, Silanemasterbatch, carbon black, and half of the Cel-Span were added to anempty barrel, and brought to a flux using both the high and medium rotorspeeds in order to maintain a melt temperature of about 360° F. The ramwas raised, the other half of the Cel-Span was added, and the mixturewas once again brought to a flux. The ram was then raised and theBurgess Clay, Epsom salt, and AX-71 were added. The ingredients weremixed for an additional 30 seconds, after the maximum torque increasewas observed. The total cycle time was about 4 minutes. The batch wasnext discharged into a downstairs hold mill at 335° F. A 4″ strip fromthe two-roll mill was next fed continuously into a short barrel extruderto form a 3″ thick continuous rope. The temperature of the rope wasrecorded to be 340° F. The extruded rope was fed to the top of aninverted L-shaped calendar to convert the molten rope into continuousthin gauge sheeting. TABLE 12 (parts per 100 parts of Escorene ™PP1105E1 and EXACT ™ 8201, combined) Escorene ™ PP 1105E1 30 (35 MFRpolypropylene homopolymer) EXACT ™ 8201 (1 MI, 0.882 density, 70ethylene-octene plastomer) Silane Masterbatch #1 3 Cel-Span NH44(non-halogen flame 20 retardant) Epsom Salt (hydrated salt for water 0.1generation) Burgess Clay 210 (filler) 3.5 ADK AX-71 (processing aid)0.75 Carbon Black 2.0 Total 129.35

The temperature profile in Table 13 below was used to produce sheetingwith a thickness of 3.8 mils, width of 58″, and at a production rate of50 yards per minute. TABLE 13 Top Roll 330-340° F. Front Roll 330-340°F. Middle Roll 330-340° F. Bottom Roll 300-310° F. Pick Off #1 Roll290-300° F. Pick Off #2 Roll 300-310° F.

The properties of the sheeting are given in Table 14 below. TABLE 14Melt Flow Rate at 10X weight (dg/min) 47.2 Thickness (mil) 3.8 50%Tensile Modulus - MD (psi) 1650 100% Tensile Modulus - MD (psi) 1790Tensile Stress @ Break - MD (psi) 2470 Elongation @ Break - MD (%) 395Gel Content (%) 32.1 Oven Aging @ 276° F. & 1 week 425% elongation

The low voltage SEM micrograph of the calendared sheeting is shown inFIG. 8. Referring now to FIG. 8, the white rugged particles arecrosslinked plastomers, and the dark lines are the polypropylene matrix.The large and small embedded particles are carbon black or flameretardant.

Example 12

A size D Banbury mixer was used to produce a TPV having a composition asdescribed in Table 15 below. EXACT™ 8201, Escorene™ PP 1105, and Silanemasterbatch were added to an empty barrel and brought to a flux usingboth the high and medium rotor speeds in order to maintain a melttemperature of about 360° F. The ram was raised and Burgess clay andEpsom salt were added. The ingredients were then mixed for an additional30 seconds, after the maximum torque increase was observed. Sunpar 150Mwas injected into the mixer to cool the melt temperature of the batch.The total cycle time was about 4 minutes. The batch was next dischargedinto a melt fed pelletizing extruder to convert the batch into ⅛″ by ⅛″pellets. TABLE 15 (parts per 100 parts of Escorene ™ PP1105E1 andEXACT ™ 8201 combined) Escorene ™ PP 1105E1 30 (35 MFR polypropylenehomopolymer) EXACT ™ 8201 (1 MI, 0.882 density, 70 ethylene-octeneplastomer) Silane Masterbatch #1 3 Epsom Salt (hydrated salt for water0.2 generation) Burgess Clay 210 (filler) 3.5 Sunpar 150M (processingoil) 12.0 Total 118.7

The pellets were then fed into the feed hopper of a Black-Clawson sheetextruder to produce 36″ width by 10 mils thick continuous sheeting underthe conditions given in Table 16. TABLE 16 Extruder Zone 1 & Zone 2 350°F. Extruder Zone 3 360° F. Extruder Zone 4 to Zone 6 380° F. Screen PackZone 1 & Zone 2 400° F. Transfer Pipe Zone 1 through 3 400° F. Melt Pump456° F.

The properties of the sheeting are given in Table 17 below. TABLE 17Melt Flow Rate at 10× weight (dg/min) 0.6 10% Tensile Modulus - MD (psi)692 50% Tensile Modulus - MD (psi) 1183 100% Tensile Modulus - MD (psi)1287 300% Tensile Modulus (psi) 1546 Ultimate Tensile Strength - MD(psi) 3745 Elongation @ Break- MD (%) 1167 Tear Strength @ Max Load - MD(lb/in) 401

Various tradenames used herein are indicated by a ™ symbol, indicatingthat the names may be protected by certain trademark rights. Some suchnames may also be registered trademarks in various jurisdictions.

All patents, test procedures, and other documents cited herein,including priority documents, are fully incorporated by reference to theextent such disclosure is not inconsistent with this invention and forall jurisdictions in which such incorporation is permitted.

1. A process for making a thermoplastic vulcanizate (TPV) in a reactor,the process comprising: a) forming a mixture in which a silane graftedresilient polymer component is dispersed in a thermoplastic matrixcomponent by mixing in the reactor: i) from 25 to 60 parts by weight ofa resilient polymer component, per 100 parts by weight of the matrixcomponent and resilient polymer component combined; ii) from 40 to 75parts by weight of the matrix component, per 100 parts by weight of thematrix component and the resilient polymer component combined; and iii)a silane grafting agent, and b) adding a solid water-generating agent tothe reactor to crosslink the silane grafted resilient polymer component.2. The process of claim 1 wherein step a) further comprises mixing afree radical generator in the reactor.
 3. The process of claim 2 whereinthe free radical generator is a peroxide.
 4. The process of claim 1wherein step a) further comprises mixing a hydrolysis catalyst in thereactor.
 5. The process of claim 2 wherein step a) further comprisesmixing a hydrolysis catalyst in the reactor.
 6. The process of claim 5wherein the silane grafting agent, free radical generator, andhydrolysis catalyst are added as individual components to the reactor.7. The process of claim 5 wherein the silane grafting agent, freeradical generator, and hydrolysis catalyst are added to the reactor as amixture on a porous carrier polymer.
 8. The process of claim 7 whereinthe porous carrier polymer is selected from the group consisting ofpolyethylene and polypropylene.
 9. The process of claim 1 wherein thesilane grafting agent is a vinylalkoxysilane.
 10. The process of claim 9wherein the vinylalkoxysilane is selected from the group consisting ofvinylmethoxysilane and vinylethoxysilane.
 11. The process of claim 1wherein the solid water-generating agent is selected from the groupconsisting of a metal oxide/carboxylic acid combination, Epsom salt,Glauber's salt, clay, water, talc, and combinations thereof.
 12. Theprocess of claim 1 wherein the matrix component comprises at least oneof a polyolefin, a polyamide, and a polyester.
 13. The process of claim1 wherein the resilient polymer component comprises at least one ofhalobutyl rubber, ethylene-propylene rubber, ethylene-propylene-dieneterpolymer rubber, natural rubber, synthetic rubber, aminefunctionalized synthetic rubber, and epoxy functionalized syntheticrubber.
 14. The process of claim 1 wherein the resilient polymercomponent is an ethylene interpolymer.
 15. The process of claim 1wherein step a) includes mixing from 25 to 35 parts by weight of theresilient polymer component and from 65 to 75 parts by weight of thematrix component, per 100 parts by weight of the matrix component andresilient polymer component combined.
 16. The process of claim 1 whereinstep a) includes mixing 30 parts by weight of the resilient polymercomponent and 70 parts by weight of the matrix component, per 100 partsby weight of the matrix component and resilient polymer componentcombined.
 17. The process of claim 1 wherein the reactor is a batch-typecompounding apparatus.
 18. The process of claim 1 wherein the reactor isa continuous-type compounding apparatus.
 19. The process of claim 1wherein the reactor is connected to a die suitable for extruding theproduct in the reactor into a shaped, fabricated product without anintervening pelletization step.
 20. The process of claim 1 wherein thematrix component has a crystallinity as determined by DSC of at least40% and the resilient polymer component has a crystallinity asdetermined by DSC of no more than 40%.
 21. The process of claim 20wherein the crystallinity of the matrix component and the resilientpolymer component differ by at least 10%.
 22. The process of claim 20wherein the crystallinity of the matrix component and the resilientpolymer component differ by at least 20%.
 23. The process of claim 1wherein the matrix component and the resilient polymer component areblended and simultaneously combined with the silane grafting agent.24-32. (canceled)